Vapor pressures and osmotic coefficients of the acetone solutions of three bis(tetraalkylammonium)tetrathiomolybdates at 298.15 K measured by head-space gas chromatography

The vapor pressures and osmotic coefficients of solutions of (R₄N)₂[MoS₄] (R = ethyl, n-propyl and n-butyl) in acetone have been measured by head space-gas chromatography (HS-GC). Experimental data for the osmotic coefficients have been expressed by three thermodynamic models including the ionic interaction model of Pitzer, the electrolyte non-random two liquid (e-NRTL) model and the non-random factor (NRF) model. The ability of the models to fit the osmotic coefficient was compared on the basis of the standard deviation of the fittings. The results show that the considered models provide reliable results, but the Pitzer's model gives better results than the NRTL and the NRF methods, especially in the dilute region.     

The effect of surfactant charge on micellization behavior

 The influence of the surfactant charge on micellization was studied on sodium n-dodecane-phosphonates, varying the charge of the surfactant ion from 0 to 2. The effects on the cmc, hydrolysis, micelle composition, and micelle ionization degree were studied. The increase of one e unit in the charge of the surfactant species reduces the cmc by about one order of magnitude. Received: 18 November 1996 Accepted: 5 March 1997     

A study of the compositional variation of the essential oil of ylang-ylang (Cananga odorata Hook Fil. et Thomson,formagenuina) during flower development

Volatile secondary metabolites from Colombian ylang-ylang flowers were obtained by combined steam distillation - solvent extraction. The samples were analyzed by high resolution gas chromatography with flame ionization, nitrogen/phosphorus, or mass spectrometric detection. The chemical composition of the oils extracted from flowers at different stages of development differed both qualitatively and quantitatively. The generation of total volatile metabolites, light oxygenated compounds in particular, increased markedly during flower maturation. In this work the quality of the ylang-ylang essential oils was studied as a function of flower maturity.     

IR spectroscopic study of the conformational lability of 4′-ethyl-4-cyanobiphenyl

The conformational lability of 4-ethyl-4-cyanobiphenyl molecules in solid crystal (SC) and isotropic liquid (IL) states was investigated by IR spectroscopic techniques (experiment and theory). IR absorption spectra were measured at 28°C–95°C in the frequency range 400 cm^–1–4000 cm^–1. Spectrum simulation was performed using the fragment method with allowance for the conformational fluctuations of molecules. The experimental and calculated spectra were compared and analyzed, and it was shown that in the IL, the samples are mixtures of conformers. The temperature changes in the spectra in the stated range are caused by the conformational lability of molecules.Original Russian Text Copyright © 2004 by L. M. Babkov, I. I. Gnatyuk, G. A. Puchkovskaya, and S. V. TrukhachevTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 3, pp. 398–405, May–June, 2004.     

Use of mobile phase 18-crown-6 to improve peak resolution between mono- and divalent metal and amine cations in ion chromatography

It is difficult to quantify NH4+ by ion chromatography in the presence of high concentrations of Na+ due to peak overlap. The Dionex IonPac CS15 column, which contains phosphonate, carboxylate, and 18-crown-6 functional groups, was originally developed to overcome this problem. We have found that the addition of 18-crown-6 to the eluent promotes improved peak resolution between Na+ and NH4+ even at concentrations as high as 60,000 to 1 using this column. Its use also improves the separation of alkali and alkaline earth metal and amine cations. Mobile phase 18-crown-6 increased the retention times of CH3NH3+, NH4+, and K+, and decreased the retention time of Sr2+. The retention times of Li+, Na+, Mg2+, Ca2+, (CH3)2NH2+, and (CH3)3NH+ were not affected. This method makes possible the direct analysis of ammonia from nitrogenase, the enzyme responsible for biological nitrogen fixation. The resolution of the NH4+ peak from the Na+ and Mg2+ peaks improved from zero resolution to values of 6.19 and 5.65, respectively. This technique considerably reduces the analysis time of NH4+ in the presence of high concentrations of Mg2+ and Na+ over traditional indophenol measurements.     

Crystallization and melting of polyethylene copolymers: Differential scanning calorimetry and atomic force microscopy studies

The Hoffman–Lauritzen theory of secondary, surface nucleation and growth was primarily relied upon for about 40 years after its introduction in about 1960 to rationalize the crystallization of flexible chain polymers into lamellar crystals. However, in about 1998, Strobl and coworkers introduced a different model for crystallization, based on the stage‐wise formation of lamellae. Two major components of this model were as follows: (1) the concept of the formation of a mesomorphic melt as a precursor to crystallization and (2) the control of the melting temperature range of lamellar crystals of homogeneous polyolefin copolymers by an inner degree of order or perfection rather than on the crystal thickness. The first concept is in disagreement with the HL theory and the second with the Gibbs‐Thomson theory, which associates melting temperature with lamella thickness. In the present study, differential scanning calorimetry and atomic force microscopy were successfully employed to monitor the in situ quiescent crystallization of polyethylene homopolymer and copolymer. In the present study, evidence was not found to support the concept of lamellae with equal thickness melting over a broad temperature range. Some evidence was found that might be interpreted to support the concept of a mesomorphic melt as a precursor to crystallization. At present, the model promoted by Strobl and coworkers appears to be at an uncertain stage at which strong proof or disproof are not available. However, this alternative model has injected a new vitality into the study of crystallization of flexible chain polymers. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2369–2388, 2006     

XPS characterization of wood chemical composition after heat‐treatment

XPS was used to characterize the chemical changes occurring after drying or applying a heat‐treatment to beech wood samples. Our results indicate that the surface of this air‐exposed material could be strongly affected either by the ambient atmosphere during storage or by the complex atmosphere in the oven during drying or heat‐treatment. However, the O/C ratio measured after removal of a thin slice of a few millimetres of an untreated sample is in reasonable agreement with that calculated from the well‐established chemical composition of beech. Through this methodology (equivalent to scraping for hard materials) it is expected to get a realistic characterization of the wood. The reliability and repeatability of the XPS measurements have been checked and the method applied to the study of the chemical changes of the beech samples subjected to heat‐treatment. Heating at 240 °C induces a significant decrease of the O/C ratio from 0.55 before to 0.44 after the treatment. Heat‐treatment induces also a decrease of the C₂ carbon contribution (carbon atom bound to a single non‐carbonyl oxygen) associated with an increase of the C₁ carbon contribution (carbon atoms bound only to carbon or hydrogen atoms), in agreement with chemical modifications reported previously in the literature. Thanks to the small analysed area of the equipment used in this study, different spots were analysed to demonstrate the presence or absence of a gradient of chemical composition due to thermal degradation or migration of extractives from within the wood structure to its surface. At the scale of our observations, the different wood samples investigated (dried or heat treated) appear to be homogeneous. Copyright © 2006 John Wiley & Sons, Ltd.     

防空兵火控雷达网及抗干扰效能评价

雷达组网作战是防空兵武器系统的发展趋势,给出了防空兵火控雷达组网的基本形式、系统组成模型和指挥控制过程,指出了火控雷达网的发展思路,构建了火控雷达网抗干扰效能综合评估指标体系,提出了火控雷达网、抗干扰效能评判方法,并通过实例分析结果表明了该模型具有实用性,为防空兵雷达组网提供辅助决策依据.     

变压器型式试验的样品组成和样品数量的确定(上)

研究和讨论了GB 19212.1-2003,5.2和附录B分别规定的单规格变压器的试验规则和"系列变压器的试验"规则,提出了确定变压器型式试验的样品组成和样品数量的一种可操作的方案.     

Influence of high pressure treatment on rheological and other properties of egg white

Abstract

The paper deals with the influence of high pressure treatment of fresh egg white on its properties and protein composition (individual amino-acids predicted as a function of pressure and time levels). The rheological properties are changed by high pressure from Newtonian to non-Newtonian behaviour, with increasing apparent viscosity as the pressure and time increased. The pH, whipping ability, foam stability, gel strength of heat induced gels after treatment and the whole protein content, were also predicted.

The results showed that the foam stability is increased with increasing pressure and time of processing. The foam volume is also increased with pressure. The pH did not change with pressure or time of processing. Composition of proteins as indicated by individual amino-acids did not exhibit statistically important changes. Gel strength of heat induced gels prepared from previously pressured liquid whites showed no important change of values with pressure or time of treatment. The modulus of elasticity showed a decrease for samples pressured to 400 MPa for 5 up to 15 minutes.